CA2429837C - Method for removing mercury from gas - Google Patents
Method for removing mercury from gas Download PDFInfo
- Publication number
- CA2429837C CA2429837C CA002429837A CA2429837A CA2429837C CA 2429837 C CA2429837 C CA 2429837C CA 002429837 A CA002429837 A CA 002429837A CA 2429837 A CA2429837 A CA 2429837A CA 2429837 C CA2429837 C CA 2429837C
- Authority
- CA
- Canada
- Prior art keywords
- mercury
- selenium
- gas
- sulphuric acid
- chlorine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052753 mercury Inorganic materials 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000007789 gas Substances 0.000 claims abstract description 39
- 239000011669 selenium Substances 0.000 claims abstract description 39
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 34
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 27
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000001117 sulphuric acid Substances 0.000 claims abstract description 19
- 235000011149 sulphuric acid Nutrition 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004291 sulphur dioxide Substances 0.000 claims abstract description 13
- 235000010269 sulphur dioxide Nutrition 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000460 chlorine Substances 0.000 claims abstract description 6
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 229940065287 selenium compound Drugs 0.000 claims description 4
- 150000003343 selenium compounds Chemical class 0.000 claims description 4
- LWJROJCJINYWOX-UHFFFAOYSA-L mercury dichloride Chemical compound Cl[Hg]Cl LWJROJCJINYWOX-UHFFFAOYSA-L 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- YQMLDSWXEQOSPP-UHFFFAOYSA-N selanylidenemercury Chemical compound [Hg]=[Se] YQMLDSWXEQOSPP-UHFFFAOYSA-N 0.000 claims description 2
- -1 selenium ions Chemical class 0.000 abstract description 4
- 150000003346 selenoethers Chemical class 0.000 abstract description 3
- 239000002244 precipitate Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000002253 acid Substances 0.000 description 10
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 description 8
- 238000001914 filtration Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 3
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002731 mercury compounds Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- QXKXDIKCIPXUPL-UHFFFAOYSA-N sulfanylidenemercury Chemical compound [Hg]=S QXKXDIKCIPXUPL-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/002—Compounds containing, besides selenium or tellurium, more than one other element, with -O- and -OH not being considered as anions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/64—Heavy metals or compounds thereof, e.g. mercury
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/48—Sulfur dioxide; Sulfurous acid
- C01B17/50—Preparation of sulfur dioxide
- C01B17/56—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/007—Tellurides or selenides of metals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/86—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by NMR- or ESR-data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/89—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by mass-spectroscopy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/32—Thermal properties
- C01P2006/33—Phase transition temperatures
- C01P2006/34—Melting temperatures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Biomedical Technology (AREA)
- Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treating Waste Gases (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Gas Separation By Absorption (AREA)
Abstract
The invention relates to a method for the removal of mercury from gas containing sulphur dioxide and oxygen and from the sulphuric acid vapour contained in the gas. According to the method, the gas is washed with a water solution that contains selenium ions, whereby metallic selenium is formed in the presence of oxygen, which precipitates the mercury in the gas and vapour either as a selenide or in a chlorine-containing environment, as a dichloride of mercury and selenium. Gas washing occurs at a low temperature, below 50 ~C.
Description
METHOD FOR REMOVING MERCURY FROM GAS
The present invention relates to a method for the removal of mercury from gas containing sulphur dioxide and oxygen and from the sulphuric acid s vapour contained in the gas. According to the method, the gas is washed with a water solution that contains selenium ions, whereby metallic selenium is formed in the presence of oxygen, which precipitates the mercury in the gas and vapour either as a selenide or, in a chlorine-containing environment, as a double chloride of mercury and selenium. Gas washing occurs at a low to temperature, below 50°C.
Sulphuric acid is usually produced from sulphur dioxide-containing gases such as those from the roasting and smelting of zinc and copper concentrates. The Hg content of gases generated in roasting is of the order is of 5 - 500 mg/Nm3. The most thorough removal of mercury from the gases is a prerequisite for the production of high quality sulphuric acid. This means that the maximum mercury content of sulphuric acid may be of the order of 0.1 mglkg H2S04.
2o The removal of mercury from gas has been carried out in many ways, which can be divided according to their operating principle into two groups. The first includes methods based on adsorption and filtration, and the second methods based on precipitation and filtration.
2s Adsorption-filtration methods are applicable only to conditions where the mercury content of the gas is low i.e. typically of the order of less than 10 mg/Nm3. In these methods the gas is routed through a filter and the mercury is adsorbed into the contact surfaces. Y-type zeolite impregnated with sulphur, active carbon and selenium filters have been used as adsorbents.
30 The use of a selenium filter is described for example in US patent 3,786,619, where the method is based on the reaction between gaseous mercury and solid selenium. An inert porous filter material is used in this method, onto which a solution containing selenium dioxide, Se02, is absorbed and dried. Selenium dioxide is reduced by the effect of the sulphur dioxide in the gas to be washed into elemental selenium, which further s reacts with the mercury forming selenides HgSe.
Precipitation-filtration methods are used in processes where the mercury charge contained in the gas is large, >_ 800 mg/Nm3. In these methods mercury is precipitated as an insoluble compound and removed from the io washers as a slurry, which is filtered. A filtration method is described for example in US patent 3.677,696, where mercury is sulphated in concentrated wash acid at temperatures of 160 - 220°C and precipitated from the circulating sulphuric acid solution. A method is known from US
patent 4,640,751, where the gases are washed with a chloride solution and is mercury is precipitated as calomel Hg2Cl2.
CA patent 934 131 presents a method whereby gases containing mercury are cleaned using 1 - 67 percent by weight sulphuric acid in temperatures of 50 - 110°C. The washing liquid used is thus a sulphuric acid solution, 2o saturated with active sulphur or selenium, present in solid form in suspension. In the connotation used here, the word active means that the compounds may be present in a very finely divided form, preferably in a freshly generated state. It is beneficial to add sulphur or selenium to the roasting gas before washing or also directly to the wash acid. Selenium may 2s be added in the form of selenium dioxide for example. When this compound comes into contact with the sulphur dioxide in the roasting gas, the sulphur dioxide reduces the selenium dioxide to elemental selenium in the diluted acid in an especially active "in situ" form. Sulphur and selenium have been found to have a surprising effect in combination. This method has made it so possible to reduce the mercury content in sulphuric acid to a value of 0.2 mg Hg/kg H2S04.
A method is known from CA patent 983 671, whereby mercury is removed from a sulphuric acid solution produced from sulphur dioxide gas by adding thiosulphate to the acid and separating the mercury sulphide thus formed, s for instance by flotation or filtration.
This invention relates to a method whereby mercury is removed from gas containing sulphur dioxide and oxygen and from the sulphuric acid vapour contained in the gas, using selenium. The well-known fact that the selenium ~o ion is easily reduced to metal by sulphur dioxide is utilised in this invention.
According to the invention, water, to which a solution containing selenium ions is added, is used as the wash water for oxygen-containing sulphur dioxide gas such as roaster gas. The reactions between the sulphur dioxide and oxygen contained in the gas and the selenium compound in the wash ~s water generate metallic selenium and sulphuric acid. In addition, sulphuric acid vapour is present in the gas. In practice it has been found that the gas coming to the acid plant from the roaster includes the majority of the mercury as dissolved in the acid vapour and only a very small fraction of it (less than 10%) is present as gaseous mercury or mercury compounds. The 2o sulphuric acid dissolves the mercury from the gases into the wash water and the dissolving mercury reacts with the selenium particles in the wash water further to form slightly soluble Se,Hg compounds. The reaction occurs at low temperatures, below 50 °C. The selenium content of the wash water is adjusted in the range 100 - 1000 mg Sell. The essential features of the 2s invention will be made apparent in the attached claims.
The reduction of the selenium compound contained in the wash water using the roaster gas can be described by the following reaction:
Se4+ + 2 S02(g) + 02 (g) + 2 H20 + 4 a =_> Se° + 4 H+ + 2 SO42- (1 ) 3o The sulphuric acid in droplet (vapour) form reacts with the selenium compound in the wash water according to the following reaction:
Se4+ + 2 S032- + 2 H20 =_> Se° + 4 H+ + 2 S042- (2) The washing of the mercury from the gas occurs with the aid of the sulphuric acid thus formed so that the mercury dissolving in the wash water further reacts to make slightly soluble Se, Hg compounds on the surface of the s selenium particles. The washing stage can be presented with a complete reaction e.g. regarding elemental mercury:
Hg + H2S04 =_> Hg2+ + S042~ + 2H+ + 2e (3) The reactions, occurring on the surface of the elemental selenium formed in io the washing, depend on whether the mercury removal is performed in a chlorine-free or chlorine-containing environment. When there is a chlorine free environment, mercury reacts on the surface of the selenium particles forming a slightly soluble mercury selenide. In a chlorine-containing environment the product is a Hg,Se double chloride. The reactions can be is expressed as follows:
Hg2+ + Se + 2e -_> HgSe (4) 3 Hg2+ + 2Se + 2C1- + 4e~ _> 2HgSe*HgCl2 (5) It has been noted in experiments that mercury removal works best when a 2o high selenium content is maintained in the wash solution, such as 100 -1000 mg Se/I. The amount of selenium is adjusted so that the selenium content is saturated in all conditions in relation to the metallic selenium formed from the liquid. The regulation of the selenium content is performed with a continuous feed. In the washing stage sulphuric acid is not added to 2s the wash solution but instead the wash liquid required for washing is pure water and the acid needed in all the reactions is either present as acid vapour in the gas or is generated as a result of the reactions of the sulphur dioxide and selenium ions in the gas. A high level of selenium and the acid produced in reaction (2) are sufficient to produce a suitable environment for 3o the effective removal of mercury. Thus the method works in almost pure water, since the acid produced by the reducing reaction of the selenium s creates the conditions whereby the elemental selenium remains (meta)stable for sufficiently long periods of time from the standpoint of mercury removal. In practice it has been found possible with the present method to produce sulphuric acid on a commercial scale with a mercury s content of less than 0.1 mg/kg H2S04.
The present invention relates to a method for the removal of mercury from gas containing sulphur dioxide and oxygen and from the sulphuric acid s vapour contained in the gas. According to the method, the gas is washed with a water solution that contains selenium ions, whereby metallic selenium is formed in the presence of oxygen, which precipitates the mercury in the gas and vapour either as a selenide or, in a chlorine-containing environment, as a double chloride of mercury and selenium. Gas washing occurs at a low to temperature, below 50°C.
Sulphuric acid is usually produced from sulphur dioxide-containing gases such as those from the roasting and smelting of zinc and copper concentrates. The Hg content of gases generated in roasting is of the order is of 5 - 500 mg/Nm3. The most thorough removal of mercury from the gases is a prerequisite for the production of high quality sulphuric acid. This means that the maximum mercury content of sulphuric acid may be of the order of 0.1 mglkg H2S04.
2o The removal of mercury from gas has been carried out in many ways, which can be divided according to their operating principle into two groups. The first includes methods based on adsorption and filtration, and the second methods based on precipitation and filtration.
2s Adsorption-filtration methods are applicable only to conditions where the mercury content of the gas is low i.e. typically of the order of less than 10 mg/Nm3. In these methods the gas is routed through a filter and the mercury is adsorbed into the contact surfaces. Y-type zeolite impregnated with sulphur, active carbon and selenium filters have been used as adsorbents.
30 The use of a selenium filter is described for example in US patent 3,786,619, where the method is based on the reaction between gaseous mercury and solid selenium. An inert porous filter material is used in this method, onto which a solution containing selenium dioxide, Se02, is absorbed and dried. Selenium dioxide is reduced by the effect of the sulphur dioxide in the gas to be washed into elemental selenium, which further s reacts with the mercury forming selenides HgSe.
Precipitation-filtration methods are used in processes where the mercury charge contained in the gas is large, >_ 800 mg/Nm3. In these methods mercury is precipitated as an insoluble compound and removed from the io washers as a slurry, which is filtered. A filtration method is described for example in US patent 3.677,696, where mercury is sulphated in concentrated wash acid at temperatures of 160 - 220°C and precipitated from the circulating sulphuric acid solution. A method is known from US
patent 4,640,751, where the gases are washed with a chloride solution and is mercury is precipitated as calomel Hg2Cl2.
CA patent 934 131 presents a method whereby gases containing mercury are cleaned using 1 - 67 percent by weight sulphuric acid in temperatures of 50 - 110°C. The washing liquid used is thus a sulphuric acid solution, 2o saturated with active sulphur or selenium, present in solid form in suspension. In the connotation used here, the word active means that the compounds may be present in a very finely divided form, preferably in a freshly generated state. It is beneficial to add sulphur or selenium to the roasting gas before washing or also directly to the wash acid. Selenium may 2s be added in the form of selenium dioxide for example. When this compound comes into contact with the sulphur dioxide in the roasting gas, the sulphur dioxide reduces the selenium dioxide to elemental selenium in the diluted acid in an especially active "in situ" form. Sulphur and selenium have been found to have a surprising effect in combination. This method has made it so possible to reduce the mercury content in sulphuric acid to a value of 0.2 mg Hg/kg H2S04.
A method is known from CA patent 983 671, whereby mercury is removed from a sulphuric acid solution produced from sulphur dioxide gas by adding thiosulphate to the acid and separating the mercury sulphide thus formed, s for instance by flotation or filtration.
This invention relates to a method whereby mercury is removed from gas containing sulphur dioxide and oxygen and from the sulphuric acid vapour contained in the gas, using selenium. The well-known fact that the selenium ~o ion is easily reduced to metal by sulphur dioxide is utilised in this invention.
According to the invention, water, to which a solution containing selenium ions is added, is used as the wash water for oxygen-containing sulphur dioxide gas such as roaster gas. The reactions between the sulphur dioxide and oxygen contained in the gas and the selenium compound in the wash ~s water generate metallic selenium and sulphuric acid. In addition, sulphuric acid vapour is present in the gas. In practice it has been found that the gas coming to the acid plant from the roaster includes the majority of the mercury as dissolved in the acid vapour and only a very small fraction of it (less than 10%) is present as gaseous mercury or mercury compounds. The 2o sulphuric acid dissolves the mercury from the gases into the wash water and the dissolving mercury reacts with the selenium particles in the wash water further to form slightly soluble Se,Hg compounds. The reaction occurs at low temperatures, below 50 °C. The selenium content of the wash water is adjusted in the range 100 - 1000 mg Sell. The essential features of the 2s invention will be made apparent in the attached claims.
The reduction of the selenium compound contained in the wash water using the roaster gas can be described by the following reaction:
Se4+ + 2 S02(g) + 02 (g) + 2 H20 + 4 a =_> Se° + 4 H+ + 2 SO42- (1 ) 3o The sulphuric acid in droplet (vapour) form reacts with the selenium compound in the wash water according to the following reaction:
Se4+ + 2 S032- + 2 H20 =_> Se° + 4 H+ + 2 S042- (2) The washing of the mercury from the gas occurs with the aid of the sulphuric acid thus formed so that the mercury dissolving in the wash water further reacts to make slightly soluble Se, Hg compounds on the surface of the s selenium particles. The washing stage can be presented with a complete reaction e.g. regarding elemental mercury:
Hg + H2S04 =_> Hg2+ + S042~ + 2H+ + 2e (3) The reactions, occurring on the surface of the elemental selenium formed in io the washing, depend on whether the mercury removal is performed in a chlorine-free or chlorine-containing environment. When there is a chlorine free environment, mercury reacts on the surface of the selenium particles forming a slightly soluble mercury selenide. In a chlorine-containing environment the product is a Hg,Se double chloride. The reactions can be is expressed as follows:
Hg2+ + Se + 2e -_> HgSe (4) 3 Hg2+ + 2Se + 2C1- + 4e~ _> 2HgSe*HgCl2 (5) It has been noted in experiments that mercury removal works best when a 2o high selenium content is maintained in the wash solution, such as 100 -1000 mg Se/I. The amount of selenium is adjusted so that the selenium content is saturated in all conditions in relation to the metallic selenium formed from the liquid. The regulation of the selenium content is performed with a continuous feed. In the washing stage sulphuric acid is not added to 2s the wash solution but instead the wash liquid required for washing is pure water and the acid needed in all the reactions is either present as acid vapour in the gas or is generated as a result of the reactions of the sulphur dioxide and selenium ions in the gas. A high level of selenium and the acid produced in reaction (2) are sufficient to produce a suitable environment for 3o the effective removal of mercury. Thus the method works in almost pure water, since the acid produced by the reducing reaction of the selenium s creates the conditions whereby the elemental selenium remains (meta)stable for sufficiently long periods of time from the standpoint of mercury removal. In practice it has been found possible with the present method to produce sulphuric acid on a commercial scale with a mercury s content of less than 0.1 mg/kg H2S04.
Claims (5)
1. A method for the removal of mercury from gas containing sulphur dioxide and oxygen and from the sulphuric acid vapour contained in the gas, wherein the gas is washed using water as the washing liquid and that a liquid selenium compound is fed into the washing liquid so that its selenium content is in the range of 100-1000 mg Se/I
at a temperature below 50° C.
at a temperature below 50° C.
2. A method according to claim 1, wherein the amount of selenium is adjusted so that the selenium content is saturated in all conditions with regard to the metallic selenium formed from the liquid.
3. A method according to claim 1, wherein the regulation of the selenium content takes place using a continuous feed.
4. A method according to claim 1, wherein in a chlorine-free environment the mercury is recovered as mercury selenide HgSe.
5. A method according to claim 1, wherein in a chlorine-containing environment the mercury is recovered as a double chloride 2HgSe*HgCl2.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FI20002698A FI117617B (en) | 2000-12-08 | 2000-12-08 | A method for removing mercury from a gas |
| FI20002698 | 2000-12-08 | ||
| PCT/FI2001/001064 WO2002045825A1 (en) | 2000-12-08 | 2001-12-07 | Method for removing mercury from gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2429837A1 CA2429837A1 (en) | 2002-06-13 |
| CA2429837C true CA2429837C (en) | 2009-09-01 |
Family
ID=8559677
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002429837A Expired - Lifetime CA2429837C (en) | 2000-12-08 | 2001-12-07 | Method for removing mercury from gas |
Country Status (17)
| Country | Link |
|---|---|
| US (1) | US7481865B2 (en) |
| EP (1) | EP1347818B1 (en) |
| JP (1) | JP2004515431A (en) |
| KR (1) | KR100840170B1 (en) |
| CN (1) | CN100366326C (en) |
| AT (1) | ATE531443T1 (en) |
| AU (2) | AU1717002A (en) |
| BR (1) | BR0116029A (en) |
| CA (1) | CA2429837C (en) |
| EA (1) | EA004577B1 (en) |
| ES (1) | ES2376993T3 (en) |
| FI (1) | FI117617B (en) |
| MX (1) | MXPA03005116A (en) |
| NO (1) | NO336277B1 (en) |
| PE (1) | PE20030633A1 (en) |
| WO (1) | WO2002045825A1 (en) |
| ZA (1) | ZA200304051B (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100836207B1 (en) * | 2001-01-18 | 2008-06-09 | 웰리켐 바이오 테크 인크. | Novel 1,2-diphenylethene derivatives for treatment of immune diseases |
| JP5040324B2 (en) * | 2007-01-17 | 2012-10-03 | 住友金属鉱山株式会社 | Method for cooling and cleaning copper smelting exhaust gas |
| JP2008190950A (en) * | 2007-02-02 | 2008-08-21 | Horiba Ltd | Removing method and removing device for selenium oxide in sample, and measuring method and measuring device for mercury in coal combustion exhaust gas using them |
| US8491865B2 (en) * | 2008-02-28 | 2013-07-23 | Brown University | Nanostructured sorbent materials for capturing environmental mercury vapor |
| EP2250014B1 (en) * | 2008-02-28 | 2019-12-04 | Brown University | Nanostructured sorbent materials for capturing environmental mercury vapor |
| US20110049045A1 (en) * | 2008-10-07 | 2011-03-03 | Brown University | Nanostructured sorbent materials for capturing environmental mercury vapor |
| CN104032137B (en) * | 2014-06-05 | 2016-06-22 | 东北大学 | A kind of method reclaiming hydrargyrum with selenides form from mercurous tailings |
| CN105056733B (en) * | 2015-07-30 | 2017-06-06 | 中南大学 | Mercury release inhibitor and its application again in a kind of flue gas during smelting washing process |
| CA3035525A1 (en) | 2016-09-02 | 2018-03-08 | Regents Of The University Of Minnesota | Systems and methods for body-proximate recoverable capture of mercury vapor during cremation |
| CN107051405B (en) * | 2017-04-10 | 2019-05-31 | 浙江工业大学 | A kind of sponge loading nanometer selenium and its chemical preparation and application |
| CN106902776B (en) * | 2017-04-10 | 2019-01-08 | 浙江工业大学 | Mercury-removing wallpaper for workshop of high-mercury industry and preparation method thereof |
| CN106975289B (en) * | 2017-04-10 | 2019-05-28 | 浙江工业大学 | A kind of high mercury workshop air clarifier core strainer and the preparation method and application thereof |
| CN115715973A (en) * | 2019-05-31 | 2023-02-28 | 贵州重力科技环保有限公司 | In-situ nano-selenium carbon-based demercuration adsorption material and preparation method and application thereof |
| CN113521979B (en) * | 2021-08-12 | 2024-01-12 | 上海交通大学 | Method for trapping mercury from sulfur-containing mercury-containing flue gas through chlorselenomel deposition |
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| SE334598B (en) | 1969-09-01 | 1971-05-03 | Boliden Ab | |
| FI45767C (en) * | 1970-07-03 | 1972-09-11 | Outokumpu Oy | Method for removing and recovering mercury and / or selenium from mercury and / or selenium-containing gases. |
| US3786619A (en) | 1971-06-04 | 1974-01-22 | Boliden Ab | Method of purifying gases containing mercury compounds and elementary mercury |
| US4057423A (en) * | 1971-09-10 | 1977-11-08 | Mitsui Mining & Smelting Co., Ltd. | Method for the manufacture of mercury free sulfuric acid |
| BE788615A (en) | 1971-09-10 | 1973-01-02 | Mitsui Mining & Smelting Co | MERCURY-FREE SULFURIC ACID PRODUCTION PROCESS |
| CA983671A (en) | 1973-05-17 | 1976-02-17 | Bo G.V. Hedenas | Method of removing mercury from sulfuric acid |
| SE403277B (en) * | 1976-04-09 | 1978-08-07 | Boliden Ab | PROCEDURES FOR WATER PURIFICATION OF GASES CONTAINING SULFUR DIOXIDE, HALOGENES AND AT LEAST ONE VOLATILE SUBJECT FROM THE GROUP INCLUDING ARSENIC AND ARSENIC ASSOCIATIONS |
| SU889071A1 (en) * | 1980-02-01 | 1981-12-15 | Всесоюзный Ордена Трудового Красного Знамени Научно-Исследовательский Горно-Металлургический Институт Цветных Металлов | Method of purifying calcining gases from mercury vapurs |
| FI62002C (en) * | 1981-04-15 | 1982-11-10 | Outokumpu Oy | REFERENCE FITTING FOR SEPARATION OF A QUANTIFIED HYDROGEN WITH HYDROGEN GASER |
| SE432361B (en) * | 1981-05-08 | 1984-04-02 | Boliden Ab | PROCEDURE FOR SEPARATION OF GASFUL ELEMENTAL MERCURY SILVER FROM A GAS |
| JPS58114728A (en) * | 1981-12-28 | 1983-07-08 | Mitsubishi Metal Corp | Mercury removing agent and its production |
| NO157543C (en) | 1984-10-19 | 1988-04-06 | Norzink As | PROCEDURE FOR PURIFICATION OF MERCURY OIL GASES AND RECOVERY OF THE MERCURY OIL IN METALLIC FORM. |
| DE4123258A1 (en) * | 1991-07-13 | 1993-01-14 | Steinmueller Gmbh L & C | METHOD FOR CLEANING A SULFUR DIOXIDE AND Possibly. OTHER EXHAUST GASES CONTAINING POLLUTANTS |
| US5480619A (en) | 1994-06-28 | 1996-01-02 | The Babcock & Wilcox Company | Regenerative scrubber application with condensing heat exchanger |
| AU3763797A (en) * | 1996-08-14 | 1998-03-06 | Noranda Inc. | Process for the removal of mercury from smelter gases |
| US6375909B1 (en) * | 2000-09-14 | 2002-04-23 | Infilco Degremont Inc. | Method for the removal of mercury and nitrogen oxides from combustion flue gas |
-
2000
- 2000-12-08 FI FI20002698A patent/FI117617B/en not_active IP Right Cessation
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2001
- 2001-11-30 PE PE2001001209A patent/PE20030633A1/en active IP Right Grant
- 2001-12-07 KR KR1020037007639A patent/KR100840170B1/en active IP Right Grant
- 2001-12-07 MX MXPA03005116A patent/MXPA03005116A/en active IP Right Grant
- 2001-12-07 CN CNB018201970A patent/CN100366326C/en not_active Expired - Lifetime
- 2001-12-07 CA CA002429837A patent/CA2429837C/en not_active Expired - Lifetime
- 2001-12-07 ES ES01999417T patent/ES2376993T3/en not_active Expired - Lifetime
- 2001-12-07 AT AT01999417T patent/ATE531443T1/en active
- 2001-12-07 EP EP01999417A patent/EP1347818B1/en not_active Expired - Lifetime
- 2001-12-07 US US10/433,844 patent/US7481865B2/en not_active Expired - Lifetime
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- 2001-12-07 WO PCT/FI2001/001064 patent/WO2002045825A1/en active Application Filing
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- 2001-12-07 JP JP2002547599A patent/JP2004515431A/en active Pending
- 2001-12-07 BR BR0116029-0A patent/BR0116029A/en not_active Application Discontinuation
- 2001-12-07 EA EA200300649A patent/EA004577B1/en not_active IP Right Cessation
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- 2003-06-03 NO NO20032507A patent/NO336277B1/en not_active IP Right Cessation
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| WO2002045825A1 (en) | 2002-06-13 |
| EA004577B1 (en) | 2004-06-24 |
| EP1347818B1 (en) | 2011-11-02 |
| NO336277B1 (en) | 2015-07-06 |
| US7481865B2 (en) | 2009-01-27 |
| PE20030633A1 (en) | 2003-08-19 |
| CA2429837A1 (en) | 2002-06-13 |
| AU1717002A (en) | 2002-06-18 |
| EA200300649A1 (en) | 2003-12-25 |
| EP1347818A1 (en) | 2003-10-01 |
| ZA200304051B (en) | 2004-02-27 |
| ATE531443T1 (en) | 2011-11-15 |
| FI20002698A0 (en) | 2000-12-08 |
| ES2376993T3 (en) | 2012-03-21 |
| US20040081605A1 (en) | 2004-04-29 |
| BR0116029A (en) | 2003-10-07 |
| KR20040010575A (en) | 2004-01-31 |
| JP2004515431A (en) | 2004-05-27 |
| MXPA03005116A (en) | 2003-09-05 |
| CN1479647A (en) | 2004-03-03 |
| KR100840170B1 (en) | 2008-06-23 |
| AU2002217170B2 (en) | 2006-07-20 |
| NO20032507D0 (en) | 2003-06-03 |
| CN100366326C (en) | 2008-02-06 |
| FI117617B (en) | 2006-12-29 |
| FI20002698A (en) | 2002-06-09 |
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